Hydroxypyridone azo dyestuffs

ABSTRACT

Disperse dyestuffs of the formula ##STR1## in which R, R 1  and R 2  denotes alkyl, 
     E denotes A or B, 
     A denotes alkyl, alkenyl, cycloalkyl or aralkyl, 
     B denotes aryl, 
     m denotes the numbers 2-4, 
     Y and Z denotes R, Cl, Br or O--E and 
     X denotes R, Cl, Br, CHO, CO--E, COO--A, CONR--E, SO 2  --E, SO 2  O--B, 
     SO 2  NR--E, CN, NO 2 , CF 3  or Y--C 6  H 4  --N═N-- with the proviso that Y and Z represent H, Cl, Br or O--E if X denotes 4-nitro, are especially suitable for the dyeing of polyester material since they give deep dyeings with high fastness to sublimation and interesting greenish-tinged yellow shade on that material.

The invention relates to new azo disperse dyestuffs, processes for their preparation and their use for dyeing hydrophobic synthetic materials.

In one of their possible tautomeric forms, the dyestuffs, which are free from sulphonic acid groups and ammonium groups, have the formula (I) ##STR2## wherein

R, R₁ and R₂ independently of one another denote hydrogen or C₁ -C₄ -alkyl,

E denotes A or B,

A denotes optionally substituted C₁ -C₈ -alkyl, C₃ -C₅ -alkenyl or cycloalkyl or carbocyclic aralkyl,

B denotes optionally substituted aryl,

m denotes the numbers 2-4,

Y and Z independently of one another denote R, Cl, Br or O-E and

X denotes R, Cl, Br, CHO, CO--E, COO--A, CONR--E, SO₂ --E, SO₂ O--B, SO₂ NR--E, CN, NO₂, CF₃ or Y--C₆ H₄ --N═N--, with the proviso that Y and Z represent H, Cl, Br or O--E if X denotes 4-nitro.

Suitable radicals R, R₁ and R₂ are, in addition to hydrogen, CH₃ and C₂ H₅, linear or branched C₃ - and C₄ -alkyl radicals.

The straight-chain or branched alkyl radicals A have 1-8 C atoms and can, for example, be monosubstituted by CN, Cl, Br, C₁ -C₄ -alkoxy, phenoxy or R--(OC₂ H₄)_(r) in which r denotes the numbers 2-4.

The preferred alkenyl radical A is the allyl radical.

Cyclohexyl or cyclopentyl radicals which are optionally substituted by methyl are suitable as cycloalkyl A.

Suitable aralkyl A is the benzyl, phenylethyl or phenylpropyl radical.

Suitable aryl B is phenyl, which can be substituted by NO₂ or monosubstituted to trisubstituted by CH₃, Cl, Br, OCH₃, OC₂ H₅ or CF₃, or 1-naphthyl.

Preferred dyestuffs are those of the formula (II) ##STR3## wherein

n denotes the numbers 2 or 3,

R₃ denotes hydrogen, CH₃ or C₂ H₅,

E' denotes A' or B',

A' denotes C₁ -C₈ -alkyl which is optionally substituted by C₁ -C₄ -alkoxy, phenoxy, Cl or R--(OC₂ H₄)_(r),

B' denotes phenyl, tolyl, chlorophenyl or dichlorophenyl,

Y' and Z' independently of one another denote hydrogen, CH₃, Cl, Br, OCH₃ or OC₂ H₅,

X' denotes Cl, Br, CN, COCH₃, COC₆ H₅, COO--A', CONR₃ --E', SO₂ CH₃, SO₂ C₆ H₅, SO₂ O--B', SO₂ NR₃ --E', phenylazo or NO₂ and

R and r have the meaning indicated above, with the proviso that Y' and Z' denote Cl, Br, OCH₃ or OC₂ H₅ if X' represents 4-nitro.

Particularly preferred dyestuffs are those of the formula (IIa) ##STR4## wherein

X" denotes Cl, COCH₃, COC₆ H₅, COO--A', CONR₃ --E', SO₂ CH₃

SO₂ O--B' or SO₂ NR₃ --E' and

Y', E', n, R₃, A' and B' have the meaning indicated above.

Suitable C₁ -C₈ -alkyl radicals A' are, for example, CH₃, C₂ H₅, n--C₃ H₇, n--C₄ H₉, n--C₅ H₁₁, n--C₆ H₁₃, n--C₈ H₁₇, i--C₃ H₇, i--C₄ H₉, CH₃ CH(C₂ H₅)C₄ H₉, i--C₈ H₁₇, CH₃ OC₂ H₄ --, CH₃ (OC₂ H₄)₂ --, C₂ H₅ OC₂ H₄ --, C₂ H₅ (OC₂ H₄)₂ --, C₂ H₅ (OC₂ H₄)₃ --, C₄ H₉ OC₂ H₄ --, C₆ H₅ OC₂ H₄ --, Cl--(CH₂)₆ --, CH₃ OC₃ H₆ --, C₂ H₅ OC₃ H₆ -- or C₆ H₅ OC₃ H₇ --.

"Bulky" radicals, such as, for example, t-butyl, are preferably located in those positions where they do not effect any steric hindrance.

The new dyestuffs of the formula (I) are obtained by either diazotising an amine of the general formula (III) ##STR5## and coupling the diazo compound with a hydroxypyridone of the general formula (IV) ##STR6## in which formulae

X, Y, Z, R, R₁, R₂, E and m have the meaning indicated above,

or reacting an azo dyestuff of the general formula (V) ##STR7## with an acylating agent of the general formula (VI) or (VII)

    O═C═N--E                                           (VI) ##STR8## in which

E has the meaning indicated above and

R₄ represents C₁ -C₄ -alkyl and

L represents halogen, preferably chlorine.

The reaction of the dyestuffs (V) with (VI) or (VII) is preferably carried out in organic solvents which are inert towards (VI)/(VII), such as, for example, acetone, methyl ethyl ketone, cyclohexanone, CH₃ CN, toluene, chlorobenzene, dichlorobenzene or nitrobenzene, optionally with the addition of acid-binding agents, such as, for example, Na carbonate or Ca carbonate, MgO, trialkylamines or pyridine.

The coupling components of the general formula (IV) are known in some cases (compare DE-OS (German Published) No. 1,956,142=British Pat. No. 1,296,857, DE-OS (German Published) No. 1,901,711=U.S. Pat. No. 3,998,803, DE-OS (German Published) No. 1,932,806=U.S. Pat. No. 3,905,951, DE-OS (German Published) No. 2,157,229=British Pat. No. 1,360,749, DE-OS (German Published) No. 2,152,536=U.S. Pat. No. 3,952,122, DE-OS (German Published) No. 1,817,977=U.S. Pat. No. 3,957,749 and Japanese Published No. 51/37,919) or are obtained in a manner which is in itself known by either reacting the hydroxypyridones of the general formula (VIII) ##STR9## which are likewise known from the literature, with an acylating agent of the formula (VI) or (VII) or--preferably--reacting a cyanoacetic acid amide of the general formula (IX) ##STR10## with an acylating agent of the formula (VI) or (VII) to give the derivatives (X) ##STR11## and then subjecting (X) to a condensation reaction with a β-ketocarboxylic acid ester of the general formula (XI) ##STR12## in a manner which is in itself known, without the use of a solvent or in, for example, an alkanol, such as methanol, ethanol, isopropanol or n-butanol, and in the presence of a base, such as, for example, KOH, NaOH, triethylamine, 2-aminoethanol, pyridine, methylamine, 3-amino-1 -propanol and the like, at elevated temperature, for example the reflux temperature, to give the hydroxypyridones (IV); in the formulae; R, R₁, R₂, R₄ and E have the meaning indicated above.

The alkali metal salts or amine salts of the coupling components which are thus obtained can be employed either direct or after neutralisation with acids, such as, for example, hydrochloric acid or acetic acid, for the coupling reaction.

Examples of amines of the formula (III) which can be used are: aniline, 2-, 3- and 4-amino-toluene, 2-, 4- and 5-amino-1,3-dimethyl-benzene, 4-amino-1,3,5-trimethyl-benzene, 4-amino-n-butyl-benzene, 3-amino-trifluoromethyl-benzene, 3- and 4-amino-1,2-dimethyl-benzene, 2,3- and 4-aminoanisole, 2,3- and 4-amino-n-butoxy-benzene, 2,3- and 4-aminophenetole, 4-amino-iso-octyl-oxy-benzene, 2-, 3- and 4-amino-diphenyl ether, 2-amino-1,4-dimethoxy-benzene, 2-amino-1,4-diethoxy-benzene, 2-amino-1,4-di-isopropoxybenzene, 2-, 3- and 4-chloroaniline, 2-, 3- and 4-bromoaniline, 2,3-, 2,4-, 2,5- and 3,4-dichloroaniline, 2,5-dibromoaniline, 2,4,5-, 2,4,6-, 3,4,5- and 3,4,6-trichloroaniline, 3-, 4-, 5- and 6-chloro-2-amino-toluene, 4-chloro-3-amino-toluene, 2-chloro-4-amino-toluene, 5-chloro-2-aminotrifluoromethyl-benzene, 4,5- and 4,6-dichloro-2-aminotoluene, 2,5- and 4,6 -dichloro-3-amino-toluene, 2,5- and 3,5-dichloro-4-amino-toluene, 4,5,6-trichloro-2-amino-toluene, 4-chloro-2-amino-1,3-dimethyl-benzene, 2-, 3- and 4-amino-benzyl-methylsulphone, 4-amino-phenyl-propyl-methylsulphone, 6-chloro-3-amino-anisole, 2-chloro-4-amino-anisole, 2-, 3- and 4-amino-benzonitrile, 1-amino-2-cyano-5-chlorobenzene, 2-chloro-4-amino-n-hexoxy-benzene, 3-chloro-4-amino-anisole, 2- and 4-nitroaniline, 5-nitro-4-amino-1,3-dimethyl-benzene, 6-nitro-3-amino-anisole, 3-nitro-4-aminoanisole, 3-nitro-4-amino-n-butoxy-benzene, 5-nitro-2-aminophenetole, 2-nitro-4-amino-phenetole, 3-nitro-4-amino-phenetole, 5-nitro-2-amino-1,4-dimethoxy-benzene, 5-nitro-2-amino-1,4-diethoxy-benzene, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 4-chloro-2-nitroaniline, 4-bromo-2-nitroaniline, 2-, 3- and 4-amino-benzaldehyde, 2-, 3- and 4-amino-diphenyl ether, 2-amino-4-chloro- and 4,4'-dichlorodiphenyl ether, 2-, 3- and 4-amino-acetophenone, 4-amino-n-butyrophenone, 4-amino-n-caprophenone, 4-amino-α-ethyl-n-caprophenone, 2-, 3- and 4-amino-benzophenone, 2-, 3- and 4-amino-4'-methyl-, -4'-isopropyl-, -4'-n-butyl- and -4'-n-hexyl-benzophenone, 2-, 3- and 4-amino-2',4'-dimethylbenzophenone, 2-, 3- and 4-amino-4'-methoxy-benzophenone, 2-, 3- and 4-amino-4'-chloro-benzophenone, methyl and ethyl 2-, 3- and 4-amino-benzoate, n-butyl 2-, 3- and 4-aminobenzoate, n-decyl 2-, 3- and 4-amino-benzoate, iso-octyl 2-, 3- and 4-amino-benzoate, cyclohexyl 2-, 3- and 4-aminobenzoate, benzyl 2-, 3- and 4-amino-benzoate, β-methoxyethyl 2-, 3- and 4-amino-benzoate, β-ethoxy-ethyl 2-, 3- and 4-amino-benzoate, β-butoxy-ethyl 2-, 3- and 4-aminobenzoate, methyl-diglycol 2-, 3- and 4-amino-benzoate, ethyl-diglycol 2-, 3- and 4-amino-benzoate, methyl-triglycol 2-, 3- and 4-amino-benzoate, ethyl-triglycol 2-, 3- and 4-amino-benzoate, β-hydroxy-ethyl 2-, 3- and 4-amino-benzoate, β-hydroxy-propyl 2-, 3- and 4-amino-benzoate, γ-hydroxy-propyl 2-, 3- and 4-amino-benzoate, δ-hydroxybutyl 2-, 3- and 4-amino-benzoate, 2-, 3- and 4-aminobenzoic acid amide, 2-, 3- and 4-amino-benzoic acid monomethylamide, 2-, 3- and 4-amino-benzoic acid iso-octylamide, 2-, 3- and 4-amino-benzoic acid dimethylamide, 2-, 3- and 4-amino-benzoic acid ethylene imide, 2-, 3- and 4-aminobenzoic acid iso-propylamide, 2-, 3- and 4-amino-benzoic acid n-hexylamide, 2-, 3- and 4-amino-benzoic acid diethylamide, 2-, 3- and 4-amino-benzoic acid di-n-butylamide, phenyl 2-, 3- and 4-amino-phenyl-sulphonate, 4'-methylphenyl 2-, 3- and 4-amino-phenyl-sulphonate, 4'-n-butylphenyl 2-, 3- and 4-amino-phenyl-sulphonate, 4'-methoxyphenyl 2-, 3- and 4-amino-phenyl-sulphonate, 4'-chlorophenyl 2-, 3- and 4-amino-phenyl-sulphonate, 4'-methylphenyl 2-, 3- and 4-amino-benzene-sulphonate, 4'-n-butylphenyl 2-, 3- and 4-amino-benzene-sulphonate, 4'-methoxyphenyl 2-, 3- and 4-amino-benzene-sulphonate, 4-amino-phenylmethylsulphone, 4-amino-phenyl-n-butylsulphone, 4-aminophenyl-iso-octylsulphone, 4-amino-diphenylsulphone, 2-, 3- and 4-amino-benzene-sulphonic acid amide, 2-, 3- and 4-aminobenzene-sulphonic acid monomethylamide, 2-, 3- and 4-aminobenzene-sulphonic acid iso-octylamide, 2-, 3- and 4-aminobenzene-sulphonic acid dimethylamide, 2-, 3- and 4-aminobenzene-sulphonic acid ethylamide, 2-, 3- and 4-amino-benzene-sulphonic acid diethylamide, 2-, 3- and 4-amino-benzenesulphonic acid di-n-butylamide, 2-, 3- and 4-amino-benzenesulphonic acid morpholide, 2-, 3- and 4-amino-benzene-sulphonic acid cyclohexylamide, 2-, 3- and 4-amino-benzenesulphonic acid anilide, 2-, 3- and 4-amino-benzene-sulphonic acid N-methyl-anilide, 1-methyl-2-amino-benzene-4-sulphonic acid amide, 1-methyl-2-amino-benzene-4-sulphonic acid n-hexylamide, 1-methoxy-2-amino-benzene-4-sulphonic acid amide, 1-methoxy-2-amino-benzene-4-sulphonic acid dimethylamide, 1-methoxy-2-amino-benzene-4-sulphonic acid di-n-butylamide, 1-methoxy-2-amino-benzene-4-sulphonic acid N-methylanilide, 1-chloro-2-amino-benzene-4-sulphonic acid dimethylamide, 1-chloro-2-amino-benzene-5-sulphonic acid β-ethoxy-ethylamide, 1-chloro-3-amino-benzene-4-sulphonic acid amide, 1-chloro-4-amino-benzene-2-sulphonic acid dimethylamide, 4-amino-azobenzene, 2',3-dimethyl-4-amino-azobenzene, 2,3'-dimethyl-4-amino-azobenzene, 2,5-dimethyl-4-amino-azobenzene, 2-methyl-5-methoxy-4-amino-azobenzene and 2',3-dimethoxy-4-aminoazobenzene.

The dyestuffs according to the invention are suitable, especially in the finely dispersed form, for dyeing and printing structures made of synthetic materials, such as, for example, polyolefines, polyvinyl compounds, cellulose 21/2-acetate, cellulose triacetate and especially polyester materials, for example polyethylene glycol terephthalate or analogous polymers. When applied by the conventional dyeing and printing processes, they give deep yellow dyeings and prints with very good fastness properties. For example, on the said types of fibre, the preferred dyestuffs of the present invention give dyeings which have an interesting greenish-tinged yellow shade and high fastness to sublimation.

In the examples which follow "parts" denote parts by weight.

EXAMPLE 1 N-(β-Hydroxyethyl)-3-cyano-4-methyl-6-hydroxy-pyrid-2-one

62.2 parts of ethanolamine are added dropwise at 10°-25° C. to 99 parts of methyl cyanoacetate. The mixture is stirred at room temperature for about a further 2 hours, 130 parts of ethyl acetoacetate are added, a further 62.2 parts of ethanolamine are then added dropwise in about 30 minutes, the mixture is heated at the boil (70°-75° C.) for 4-5 hours and the alcohols formed are then distilled off until a bottom temperature of at most 120° C. is reached. The dark brown, oily residue is diluted with water and the pH is adjusted to 7 with HCl.

According to the determination of the coupling value, this solution, which can be employed in this form for the synthesis of the dyestuff, contains 92-96% of theory of the desired product; only traces of impurities can be discerned by thin layer chromatography.

For isolation, only a small amount of water is added and the pH is adjusted to 2 with HCl; the bulk of the product then precipitates out and can be filtered off. Melting point 168°-170° C. (colourless needles after recrystallisation from water).

At lower pH values the hydrochloride is isolated: colourless needles on recrystallisation from water; sintering with a brown colouration above about 170° C., decomposition temperature 220° C.

The cyclisation can also be carried out in methanolic solution using KOH as an auxiliary base; in this case the K salt of the pyridone precipitates out.

EXAMPLE 2 ##STR13##

62.2 parts of ethanolamine are added dropwise at 10°-25° C. to 99 parts of methyl cyanoacetate. The mixture is stirred at room temperature for a further 1 hour and the methanol formed during the reaction is then distilled off under a water pump vacuum at a bottom temperature of at most 80° C., and 110 parts of n-butyl isocyanate are added rapidly dropwise at about 80° C.: initially there are two phases, which are converted to a homogeneous product by stirring for 2 hours at 105°-110° C.

At 80°-90° C., 130 parts of ethyl acetoacetate are then added rapidly and 62.2 parts of ethanolamine are added slowly.

The mixture is stirred for 5 hours at about 100° C. and is then discharged into about 1,000 parts of ice-water/300 parts of concentrated HCl: the product, which initially is oily, soon crystallises completely and is filtered off, washed with water and--if necessary--dried; according to thin layer chromatography it contains only traces of impurities.

Yield: about 220 parts (75% of theory)

Melting point 136° C. and after recrystallisation from H₂ O 143° C.

EXAMPLE 3

15.1 parts of methyl p-aminobenzoate are dissolved in 60 parts of water and 30 parts of concentrated HCl and, after adding 100 parts of ice, diazotised at 0°-3° C. by the dropwise addition of one equivalent of 30% strength NaNO₂ solution. A little amidosulphonic acid is then added and if necessary the solution is clarified by the addition of 10 parts of kieselguhr.

19.4 parts of N-(β-hydroxyethyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one are dissolved in about 200 parts of water with the addition of 40% NaOH, at pH 7-8. The mixture is cooled to 3°-8° C. by adding about 200 parts of ice and the above diazotisation mixture is allowed to run into this solution. During the addition, the pH value is kept at pH 5 by adding 40% strength NaOH dropwise at the same time, the mixture is then stirred for about a further 1 hour and, after filtering, washing the product with water and drying, about 34 parts (95% of theory) of the greenish-tinged yellow dyestuff are obtained.

This is boiled under reflux in about 300 parts of chlorobenzene with 10 parts of n-butyl isocyanate for 4-5 hours; according to thin layer chromatography the reaction has then ended. After cooling to room temperature, filtering, washing the product with methanol and drying, about 41 parts (90% total yield) of the dyestuff of the formula ##STR14## are obtained; this dyestuff dyes polyester fibres, for example, in a greenish-tinged yellow shade with outstanding fastness properties.

EXAMPLE 4

16.2 parts of 3,4-dichloroaniline are diazotised in aqueous/hydrochloric acid solution with NaNO₂ solution, by the procedure described in Example 3. The solution thus obtained is allowed to run into a suspension, which has been cooled to 3°-5° C., of 29.5 parts of the coupling component described in Example 2 in about 300 parts of water, the pH value being kept at pH 5 during the addition by adding 40% strength NaOH dropwise, and the mixture is then stirred for 3-4 hours. After filtering, washing the product with water and drying, about 44 parts (94% of theory) of the dyestuff of the formula ##STR15## are obtained; this dyestuff dyes polyester materials, for example, in greenish-tinged yellow shades with outstanding fastness properties.

EXAMPLE 5

19.4 parts of dried N-(β-hydroxyethyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one and 11 parts of n-butyl isocyanate in about 200 parts of diisopropyl ketone are heated at the boil for 5 hours. The solvent is then distilled off, the residue is taken up in about 300 parts of water, 200 parts of ice are added and a solution of diazotised o-nitroaniline, which has been prepared from 13.8 parts of o-nitroaniline by the procedure described in Example 3, is allowed to run in. During the addition, the pH is kept at 4.5-5.5 by adding 40% strength NaOH dropwise. After the coupling reaction has taken place, the reaction mixture is stirred for a further 4 hours and filtered, the material on the filter is washed with water and the dyestuff of the formula ##STR16## which is thus obtained is dried (about 40 g, 94% of theory). It dyes polyester materials, for example, in greenish-tinged yellow shades of outstanding fastness.

The dyestuffs listed in the tables which follow are prepared analogously to the above examples and serve to illustrate the present invention.

                                      TABLE 1                                      __________________________________________________________________________      ##STR17##                                                                     Ex-                                                                            ample                                                                          No.   X            E       m Shade                                             __________________________________________________________________________     6   4-C.sub. 8 H.sub.17 OOC                                                                     CH.sub.3  2 greenish-                                                                      tinged yellow                                     7   "            C.sub.2 H.sub.5                                                                          3 greenish-                                                                      tinged yellow                                     8   "            C.sub.2 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     9   "            m-CH.sub.3C.sub.6 H.sub.4                                                                3 greenish-                                                                      tinged yellow                                     10  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     11  "            CH.sub.2C.sub.6 H.sub.5                                                                  2 greenish-                                                                      tinged yellow                                     12  "            C.sub.4 H.sub.9                                                                          3 greenish-                                                                      tinged yellow                                     13  "            CH.sub.2CHCH.sub.2                                                                       2 greenish-                                                                      tinged yellow                                     14  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     15  "            i-C.sub.4 H.sub.9                                                                        2 greenish-                                                                      tinged yellow                                     16  "            (CH.sub.3).sub.2 C.sub.6 H.sub.5                                                         2 greenish-                                                                      tinged yellow                                     17  4-C.sub. 6 H.sub.13 OOC                                                                     CH.sub.3  2 greenish-                                                                      tinged yellow                                     18  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     19  "            i-C.sub.4 H.sub.9                                                                        2 greenish-                                                                      tinged yellow                                     20  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     21  "            C.sub.4 H.sub.9                                                                          3 greenish-                                                                      tinged yellow                                     22  4-C.sub. 4 H.sub.9 OOC                                                                      CH.sub.3  2 greenish-                                                                      tinged yellow                                     23  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     24  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     25  "            C.sub.2 H.sub.5                                                                          3 greenish-                                                                      tinged yellow                                     26  4-C.sub.3 H.sub.7 OOC                                                                       CH.sub.3  2 greenish-                                                                      tinged yellow                                     27  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     28  "            o-CH.sub.3C.sub.6 H.sub.4                                                                2 greenish-                                                                      tinged yellow                                     29  "            CH.sub.3  3 greenish-                                                                      tinged yellow                                     30  4-C.sub. 2 H.sub.5 OOC                                                                      C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     31  "            C.sub.6 H.sub.13                                                                         2 greenish-                                                                      tinged yellow                                     32  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     33  4-CH.sub. 3 OOC                                                                             CH.sub.3  2 greenish-                                                                      tinged yellow                                     34  "            i-C.sub.4 H.sub.9                                                                        2 greenish-                                                                      tinged yellow                                     35  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     36  4-CH.sub. 3 OC.sub.2 H.sub.4 OOC                                                            CH.sub.3  2 greenish-                                                                      tinged yellow                                     37  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     38  "            C.sub.6 H.sub.13                                                                         2 greenish-                                                                      tinged yellow                                     39  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     40  "            C.sub.4 H.sub.9                                                                          3 greenish-                                                                      tinged yellow                                     41  4-CH.sub.3 (OC.sub.2 H.sub.4).sub.2 OOC                                                     C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     42  "            C.sub.3 H.sub.7                                                                          2 greenish-                                                                      tinged yellow                                     43  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     44  2-C.sub.6 H.sub.13 OOC                                                                      C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     45  2-C.sub. 2 H.sub.5 OOC                                                                      C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     46  2-C.sub.4 H.sub.9 OOC                                                                       CH.sub.3  3 greenish-                                                                      tinged yellow                                     47  4-CH.sub. 3 NHOC                                                                            CH.sub.3  2 greenish-                                                                      tinged yellow                                     48  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     49  4-C.sub. 2 H.sub.5 NHOC                                                                     CH.sub.3  2 greenish-                                                                      tinged yellow                                     50  "            i-C.sub.4 H.sub.9                                                                        2 greenish-                                                                      tinged yellow                                     51  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     52  "            CH.sub.2C.sub.6 H.sub.5                                                                  3 greenish-                                                                      tinged yellow                                     53  4-C.sub. 4 H.sub.9 NHOC                                                                     C.sub.2 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     54  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     55  "            p-CH.sub.3C.sub.6 H.sub.4                                                                2 greenish-                                                                      tinged yellow                                     56  4-C.sub. 6 H.sub.13 NHOC                                                                    CH.sub.3  2 greenish-                                                                      tinged yellow                                     57  "            C.sub.3 H.sub.7                                                                          2 greenish-                                                                      tinged yellow                                     58  4-C.sub. 8 H.sub.17 NHOC                                                                    CH.sub.3  2 greenish-                                                                      tinged yellow                                     59  "            C.sub.2 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     60  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     61  "            C.sub.4 H.sub.9                                                                          3 greenish-                                                                      tinged yellow                                     62  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     63  4-(C.sub. 2 H.sub.5).sub.2 NOC                                                              C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     64  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     65  "            CH.sub.2C.sub.6 H.sub.5                                                                  2 greenish-                                                                      tinged yellow                                     66  4-C.sub. 8 H.sub.17 NHO.sub.2 S                                                             CH.sub.3  2 greenish-                                                                      tinged yellow                                     67  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     68  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     69  "            C.sub.2 H.sub.5                                                                          3 greenish-                                                                      tinged yellow                                     70  "            m-CH.sub.3C.sub.6 H.sub.4                                                                2 greenish-                                                                      tinged yellow                                     71  4-C.sub. 6 H.sub.13 NHO.sub.2 S                                                             i-C.sub. 3 H.sub.7                                                                       2 greenish-                                                                      tinged yellow                                     72  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     73  "            m-CH.sub.3C.sub.6 H.sub.4                                                                2 greenish-                                                                      tinged yellow                                     74  4-C.sub. 4 H.sub.9 NHO.sub. 2 S                                                             C.sub.2 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     75  "            CH.sub.3  2 greenish-                                                                      tinged yellow                                     76  4-C.sub. 2 H.sub.5 NHO.sub.2 S                                                              CH.sub.3  2 greenish-                                                                      tinged yellow                                     77  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     78  "            CH.sub.2C.sub.6 H.sub.5                                                                  2 greenish-                                                                      tinged yellow                                     79  4-(C.sub. 2 H.sub.5).sub.2 NO.sub.2 S                                                       CH.sub.3  2 greenish-                                                                      tinged yellow                                     80  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     81  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     82  4-CH.sub. 3 O.sub.2 S                                                                       C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     83  4-C.sub. 6 H.sub.5 O.sub.2 S                                                                CH.sub.3  2 greenish-                                                                      tinged yellow                                     84  4-C.sub. 6 H.sub.5 OO.sub.2 S                                                               CH.sub.3  2 greenish-                                                                      tinged yellow                                     85  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     86  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     87  4-C.sub. 6 H.sub.5 NHO.sub.2 S                                                              CH.sub.3  2 greenish-                                                                      tinged yellow                                     88  "            C.sub.4 H.sub.9                                                                          3 greenish-                                                                      tinged yellow                                     89  4-C.sub. 6 H.sub.5 NHOC                                                                     CH.sub.3  2 greenish-                                                                      tinged yellow                                     90  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     91  4-CH.sub. 3 CO                                                                              CH.sub.3  2 greenish-                                                                      tinged yellow                                     92  "            C.sub.2 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     93  "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     94  "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     95  4-C.sub. 6 H.sub.5 CO                                                                       CH.sub.3  2 greenish-                                                                      tinged yellow                                     96  "            i-C.sub.3 H.sub.7                                                                        2 greenish-                                                                      tinged yellow                                     97  "            CH.sub.3  3 greenish-                                                                      tinged yellow                                     98  2-NO.sub. 2  CH.sub.3  2 greenish-                                                                      tinged yellow                                     99  "            i-C.sub.3 H.sub.7                                                                        2 greenish-                                                                      tinged yellow                                     100 "            i-C.sub.4 H.sub.9                                                                        2 greenish-                                                                      tinged yellow                                     101 "            C.sub.4 H.sub.9                                                                          3 greenish-                                                                      tinged yellow                                     102 "            C.sub.6 H.sub.13                                                                         2 greenish-                                                                      tinged yellow                                     103 "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     104 "            CH.sub.2C.sub.6 H.sub.5                                                                  2 greenish-                                                                      tinged yellow                                     105 "            m-CH.sub.3C.sub.6 H.sub.4                                                                2 greenish-                                                                      tinged yellow                                     106 4-NO.sub. 2  CH.sub.3  2 yellow                                            107 "            C.sub.4 H.sub.9                                                                          2 yellow                                            108 "            C.sub.6 H.sub.5                                                                          2 yellow                                            109 2-CN         C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     110 4-CN         i-C.sub.3 H.sub.7                                                                        2 greenish-                                                                      tinged yellow                                     111 2-Cl         C.sub.4 H.sub. 9                                                                         2 greenish-                                                                      tinged yellow                                     112 "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     113 3-Cl         C.sub.2 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     114 "            o-CH.sub.3C.sub.6 H.sub.4                                                                2 greenish-                                                                      tinged yellow                                     115 4-Cl         CH.sub.3  2 greenish-                                                                      tinged yellow                                     116 "            CH.sub.3  3 greenish-                                                                      tinged yellow                                     117 "            C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     118 "            C.sub.6 H.sub.13                                                                         2 greenish-                                                                      tinged yellow                                     119 "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     120 2-Br         C.sub.2 H.sub.5                                                                          3 greenish-                                                                      tinged yellow                                     121 "            C.sub.6 H.sub.5                                                                          2 greenish-                                                                      tinged yellow                                     122 2-CF.sub. 3  C.sub.4 H.sub.9                                                                          2 greenish-                                                                      tinged yellow                                     123 4-C.sub. 6 H.sub.5NN                                                                        CH.sub.3  2 golden                                                                         yellow                                            124 "            C.sub.4 H.sub.9                                                                          2 golden                                                                         yellow                                            __________________________________________________________________________

                  TABLE 2                                                          ______________________________________                                          ##STR18##                                                                     Ex-                                                                            ample                                                                          No.   X        Y         E        m   Shade                                    ______________________________________                                         125    4-NO.sub.2                                                                              2-OCH.sub.3                                                                             CH.sub.3 2   yellow                                   126   "        "         C.sub.4 H.sub.9                                                                         2   yellow                                   127   "        "         C.sub.6 H.sub.5                                                                         3   yellow                                   128   "        2-OC.sub.2 H.sub.5                                                                       i-C.sub.4 H.sub.9                                                                       2   yellow                                   129   "        2-OC.sub.6 H.sub.5                                                                       CH.sub.3 2   yellow                                   130   2-Cl     3-Cl      C.sub.4 H.sub.9                                                                         2   greenish-                                                                      tinged yellow                            131   "        "         C.sub.6 H.sub.5                                                                         2   greenish-                                                                      tinged yellow                            132   "        "         CH.sub.3 2   greenish-                                                                      tinged yellow                            133   "        4-Cl      CH.sub.3 2   greenish-                                                                      tinged yellow                            134   "        "         C.sub.4 H.sub.9                                                                         3   greenish-                                                                      tinged yellow                            135   "        "         C.sub.6 H.sub.5                                                                         2   greenish-                                                                      tinged yellow                            136   "        5-Cl      CH.sub.3 2   greenish-                                                                      tinged yellow                            137   "        "         C.sub.4 H.sub.9                                                                         2   greenish-                                                                      tinged yellow                            138   "        "         C.sub.6 H.sub.5                                                                         2   greenish-                                                                      tinged yellow                            139   "        "         CH.sub.2C.sub.6 H.sub.5                                                                 3   greenish-                                                                      tinged yellow                            140   "        "         i-C.sub.3 H.sub.7                                                                       2   greenish-                                                                      tinged yellow                            141   2-Br     5-Br      CH.sub.3 2   greenish-                                                                      tinged yellow                            142   "        "         C.sub.4 H.sub.9                                                                         2   greenish-                                                                      tinged yellow                            143   2-Cl     4-CH.sub.3                                                                               C.sub.4 H.sub.9                                                                         2   greenish-                                                                      tinged yellow                            144   "        5-CH.sub. 3                                                                              "        2   greenish-                                                                      tinged yellow                            145   "        3-CH.sub.3                                                                               "        2   greenish-                                                                      tinged yellow                            146   3-Cl     4-Cl      CH.sub.3 2   greenish-                                                                      tinged yellow                            147   "        "         i-C.sub.3 H.sub.7                                                                       2   greenish-                                                                      tinged yellow                            148   "        "         C.sub.6 H.sub.13                                                                        2   greenish-                                                                      tinged yellow                            149   "        "         C.sub.6 H.sub.5                                                                         3   greenish-                                                                      tinged yellow                            150   3-Cl     5-Cl      CH.sub.3 3   greenish-                                                                      tinged yellow                            151   "        "         C.sub.4 H.sub.9                                                                         2   greenish-                                                                      tinged yellow                            152   "        "         CH.sub.2C.sub.6 H.sub.5                                                                 2   greenish-                                                                      tinged yellow                            153   "        "         C.sub.6 H.sub.5                                                                         2   greenish-                                                                      tinged yellow                            154   2-Cl     5-CN      CH.sub.3 2   greenish-                                                                      tinged yellow                            155   "        "         C.sub.4 H.sub.9                                                                         2   greenish-                                                                      tinged yellow                            156   2-NO.sub. 2                                                                             4-OCH.sub. 3                                                                             CH.sub.3 2   golden                                                                         yellow                                   157   "        "         C.sub.4 H.sub.9                                                                         3   golden                                                                         yellow                                   158   "        4-OC.sub.6 H.sub.5                                                                       C.sub.4 H.sub.9                                                                         2   golden                                                                         yellow                                   159   4-Cl     2-NO.sub.2                                                                               CH.sub.3 2   golden                                                                         yellow                                   160   "        "         C.sub.4 H.sub.9                                                                         2   golden                                                                         yellow                                   161   "        "         C.sub.6 H.sub.5                                                                         3   golden                                                                         yellow                                   162   4-NO.sub. 2                                                                             2-Cl      C.sub.4 H.sub.9                                                                         2   golden                                                                         yellow                                   163   "        "         C.sub.6 H.sub.5                                                                         2   golden                                                                         yellow                                   164   4-Cl     3-CH.sub.3                                                                               CH.sub.3 2   greenish-                                                                      tinged yellow                            165   "        "         C.sub.4 H.sub.9                                                                         2   greenish-                                                                      tinged yellow                            166   "        "         C.sub.4 H.sub.9                                                                         3   greenish-                                                                      tinged yellow                            167   "        2-CH.sub. 3                                                                              C.sub.4 H.sub.9                                                                         2   greenish-                                                                      tinged yellow                            168   "        "         C.sub.6 H.sub.5                                                                         2   greenish-                                                                      tinged yellow                            169   3-Cl     4-CH.sub.3                                                                               CH.sub.3 2   greenish-                                                                      tinged yellow                            170   "        "         C.sub.4 H.sub.9                                                                         2   greenish-                                                                      tinged yellow                            ______________________________________                                    

                  TABLE 3                                                          ______________________________________                                          ##STR19##                                                                     Ex-                                                                            am-                                                                            ple                                                                            No.  X        Y        Z      E     m   Shade                                  ______________________________________                                         171  2-Cl     4-Cl     5-CH.sub. 3                                                                           CH.sub.3                                                                             2   greenish-                                                                      tinged yellow                          172  "        "        "      C.sub.4 H.sub.9                                                                      2   greenish-                                                                      tinged yellow                          173  "        "        "      C.sub.6 H.sub.5                                                                      2   greenish-                                                                      tinged yellow                          174  "        "        "      i-C.sub.4 H.sub.9                                                                    2   greenish-                                                                      tinged yellow                          175  "        "        "      CH.sub.3                                                                             3   greenish-                                                                      tinged yellow                          176  2-CH.sub. 3                                                                             4-NO.sub.2                                                                              5-Cl   CH.sub.3                                                                             2   golden yellow                          177  "        "        "      C.sub.4 H.sub.9                                                                      2   golden yellow                          178  2-Cl     4-CH.sub.3                                                                              5-CH.sub.3                                                                            CH.sub.3                                                                             2   greenish-                                                                      tinged yellow                          179  "        "        "      C.sub.2 H.sub.5                                                                      2   greenish-                                                                      tinged yellow                          180  "        "        "      C.sub.4 H.sub.9                                                                      2   greenish-                                                                      tinged yellow                          181  4-Cl     2-CH.sub.3                                                                              5-CH.sub.3                                                                            C.sub.4 H.sub.9                                                                      2   greenish-                                                                      tinged yellow                          182  "        "        "      C.sub.6 H.sub.5                                                                      3   greenish-                                                                      tinged yellow                          183  2-Cl     4-Cl     5-Cl   CH.sub.3                                                                             3   greenish-                                                                      tinged yellow                          184  "        "        "      C.sub.4 H.sub.9                                                                      2   yellow                                 185  "        "        "      C.sub.6 H.sub.5                                                                      2   yellow                                 ______________________________________                                     

We claim:
 1. An azo disperse dyestuff of the formula ##STR20## in which E is C₁ -C₄ -alkyl,X is H, Cl or NO₂, Y is H, Cl, Cl₁ -C₄ -alkyl, OCH₃ or OC₆ H₅, and Z is H or Cl,with the proviso that when X is H or Cl both Y and Z are Cl.
 2. An azo dyestuff according to claim 1, in which X is H or Cl.
 3. An azo dyestuff according to claim 1, in which X is H and E is n--C₄ H₉.
 4. An azo dyestuff according to claim 1, in which X is NO₂. 